Disposal of refinery wastes



Jam. 9, 1945. P. E. MALsoN DISPOSAL OF REFINERY WS'IESV v Filed May 25,l 1942 E mmn.

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drocarben.nistillateszand Miel. f- "kyl onenols, preferably I:at about .notrrlal Patented Jan..9, 1945 assigne msiaosnL-'or mummy nostros :Parker MalsortLEa-St Alten, 1.111., 4Shell rnwelopment Company, .San Francisco,

-Galipacorporation of Delaware' @msg atignMafyQzs, iafizsserielno.@44,419

,comme (c1. ,25a-e627) This inyention deals `with av method fior @Se posing of. petroleum -renery wastes and ,simul- .taneously recovering y'valuable products.. kMore fable alkyl v.phenols canfbe ,recoteredgat mo entre .expense of chemicals withthe; simultaneous fpmduction of unobjectionable efliuent which :can the disposed into sewers. f

It :is afpurpose :ofslthis invention sto dispose ofr i v y particularly, it dealsgwith:apombination process in which spentaqueous caustic s'aillia'li 'and uva-ste acids arecombined in such am'anner atlilatk Nahl- Xwaste .caustic alka'lirinqsuchawayfas rtogproduce :a sewer water v'reearom obiectionable matter'- *It is another :purpose simultaneouslyatogreceyer :valuable xalkylzphenols sand HzS :fromzwastealls- ,t tic. 'It is -still anotherpurposefto mtiliz @Ste acids such :as :sludge 1 acids obtained :in :the frefnf .ing vof hydrocarbons, which acids containorsarric Y.vnriatter for neutraliaing the waste alkali( in 'auch la way as sto ,liberatealkyljmhenels iareinot fMy .inwention comprises treat temperature, with@ streng ecus `seluti caustie alkali, 1i. et, alkali metalfhydrexide. vitfhere- @Y 1a "Spent aqueous Solution is produced sentaising y.alkali lmetal ,alkyl ,.nhenelatesfseturati-nsthis timone is withdrawn through :iinesfand dpariiany spent sodiumr vhydroxide solution containing alkyl :phenolates fiszpumped by pumped; through-line .1.

` A portionof Ithis solution iis reoircula'ted through line `2 incombnation Withjlfresh iNaQH; and `-the :remainder of 'the at vfleast partially spent solution passes through fline i3 .to tank l L61 .or Yas an alternativzethough iline" to vmeet v`sour naphtha vlcontaining HzS in linefl. v*'{Ihe mixture resulting `from `the second a'lterhaitiife ipasseslth-rough mixer 2l 0 `finto settler A.I I. L'Ireated snaphtha fis .withdrawn through 'line 1f2- and spent` aqueouszNaGH solution is pumped rloygpump 43 through linerM,

' :a :portion .returningfto vmixer `lil and the lremain- Solution fwitfh :Has produced :within the process to liberate the phenolsfseparating Ithe iphenols thereafter "contacting lthe remaining aqueous solution with waste acid such as acidjsludge produced in refinery operations', funder conditions such that r`I-IiS is liberated which -is reci-rculated y:into theprocess to vliberate zphenolsfand anaque- .ous saltsolutionis produced lnormallyco1itatn ing )suspended organic-material. A Thissolution .is-al-` lowed to settle to remove vtlie org-anicmatter, gf' present, and the -salt solution is then -runito .the sewers. My yprocess is ,Plied flow `diagram of :an 'actual'plant-installation.V Referring `,to `the .d-rawins, :pressure .distillate y P l1.) Containing alkyl p nels-:mercapztans, H28; eta, enters .the :su

line I. The pressure distillate isi-m strong aqueous sodium hydroxide v-`introduced through line 2 in mixer 3, and the mixture is allowed to separate in settler 4. `Treated disfmerze .readily understood from the accompanying drawing representing Aa sim-- a5 through v lxed with hder .going through line vt5 to storagetank fl-5.

yCare should ibe f ltaken `thatv the amount 4of :taken -up vfromfthe sour naphtha .isnot '-sui'licient to Vfspring the fphenols alreadyfpreserit ithe NaOH solution lfrom settler/ligas .otherwise the Iyield of alkyl v=plieno1s ithelsubsequentarecoven'y step'would befreduced v`From this itan'k, l'the Vspent .solution then :prolc eeds through iline li1 to contact-tower v18, where -it lis contacted, -preterablylat about normal room temperature =wi-th 1an amount lof ywhich may Iloe in fexcessof 4that y.which :can ibe italien up 'iby the aqueous solution. Excess HzkS, if any, `.passes through top ilineilS, While aqueous sodium/sulde Ysolution saturated twith vI-IsS iproceeds through line Z0 to settler 12 I, ftogether with alkyl :phenols 'liberated by the Hes. `Thephencilsiarehallowed fto separate.

The amount of H28 xused-in fthe sstep of liberat- `ing alkjyl xphenols'1 should not :.beriless than .that

`required -to impart `l:to vithe Is'o'li-ition .aipH -nalue'r of 855 'or fslightly ilower, which'jpoint .can easilytbe recognized :with -the faid iofjphenolphthalein vindicator. If the pH values-.isfhiglher, none .ora v'portion only of the alkyl phenols :may ibe lli-berated, and also those vWllfiich'areliberated 'contain substantial amounts of alkali which isundesirf able. Y

y'lhe remaining, agueous solution substantially :free .from alkyl phenols now Vproceeds l:through ibottom line 23 and is admired with `fan,willst auf .Waste iacidfintroduced through line f2-4, "he

mixture passes through mixer 25 and is then introduced intotIzS-s'eerater 26 wherein the waste acid generates 'I-IzS, the flatter fgoing through line 21 `to tower I8. The amount of sulfides which are highly objectionable components of sewer Water. If desired, the waste liquor may be heated to drive out HzS more corn- 4 pletely.

If more H2S is produced in generator 26` than is needed for the liberation of the alkyl phenols, excess may be withdrawn through line 32. o

Ii the disposal of excess I-I2S as part of the sewer water in the form of sodium sulfide is permissible, an automatic regulation of the amount of waste acid introduced through line 24 may be governed by the pressure of H25 in the top of the contact tower I8 through connection 33 and automatic valve 34. By this means, only sufiicient sludge acid is introduced through line 24 to release the exact amount of H25 required to spring the alkyl phenols. It is convenient to set the regulator to maintain an HzS pressure in the contact tower I8 of about -lit/in.2 gauge.

The resulting salt water, which is preferably substantially free from suliides but may contain organic matter, is withdrawn through bottom line 28 and passes to separator 29 wherein the organic matter, such as sludge oil, is settled out and withdrawn through line 3d. The salt water substantially free of organic matter emerges through line 3| and goes to the sewer.

The described process has several advantages. In the first place, it makes possible a substantially complete utilization of the caustic needed in treating cracked and straight-run naphtha. It makes possible the utilization of waste acid for neutralizing spent caustic in such a manner that phenols and HzSl can be separately recovered. It makesl possible the production of a waste water which is substantially free frornobnoxious.materials which, if present, would make disposal of the waste water through sewer systems objectionable; and further, it makes possible the separate disposal of sludge oil which is present in the waste acid.

Acids used for liberating HzS from the sulde solution produced in the process may comprise various water-soluble acids stronger than H28. I prefer to use sludge acids, such as are obtained in the treatment of aviation gasolines, cracked distillates, lubricating oils, etc., with sulfuric acid, or may comprise spent alkylation acids or other strong mineral acids used in Various reiining processes, such as phosphoric acid sludges that are produced in certain special refinery operations, aqueous hydrochloric acid, etc.

Below are some typical operating data of a plant installation in actual operation:

Pressure Temperpsi ature pH gauge F Contact tank 18 5-10 40-100 8. 2 20-35 40-100' 8. 2 115-150 6. 0-7. 0

` Typical properties of the aqueous solution during various stages of the process are shown in the table below:

As Will be noted, in the above process two types of highly obnoxious waste products can be disposed in a manner to yield a single waste water free from compounds which cannot safely be run to the sewers. Simultaneously, valuable phenols are produced free from organic matter which Would contaminate them if the spent caustic alkali solution were directly neutralized with sludge acid. As a. further by-product, HQS is obtained. l

Thus, the alkyl phenols recovered by this process, while usually of high sulfur content, are of suicient purity so that they can be used as such for many purposes; or else they can be desulfurized by standard methods for the desulfurization of alkyl phenols, such as air blowing in the acid state, or in alkaline aqueous solutions and separating products of oxidation.

I claim as my invention:

1. In a process for recovering alkyl phenols from hydrocarbon oils containing them and hydrogen sulfide and simultaneously disposing of Waste products, the steps comprising treating said hydrocarbonoils with an aqueous alkali metal hydroxide solution to produce a solution containing alkyl phenolates, contacting the latter with HzS in an amount. suiicient to liberate alkyl phenols, separating liberated alkyl phenols, adding to the remaining aqueous solution a sludge acid containing organic matter resulting from treatment of hydrocarbons with a sulfuric. acid, said sludge acid being added in an amount suincient to form a neutral solution, whereby a salt solution is produced containing said organic matter in suspension and gaseous HzS is liberated. returning liberated HzS to said contacting step, separating said organic matter from said salt solution, and separately withdrawing the latter.

2. The process of claim l. wherein said amount of acid added to said solution is automatically during said contact step.

3. The process of claim 1 wherein said amount of acid added to said solution is automatically regulated to maintainbetween about 5 and l5 pounds per square inch pressure gauge of HaS employed during said contact step.

4. The process of claim l wherein the amount of HzS to liberate said alkyl phenols is sufficient to reduce the pH Value of said solution 'to below 8.5.

5f The process of claim l wherein said salt solution is heated to drive out dissolved HQS.

6. The process of claim 1 wherein said salt solution is heated to about 150 F. to drive out dissolved HzS.

PARKER E. MALSQN. 

